Ruthenium dihydrogen complex for C-H activation: Catalytic H/D exchange under mild conditions

Martin H G Prechtl, Markus Hölscher, Yehoshoa Ben-David, Nils Theyssen, David Milstein, Walter Leitner

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Abstract

Catalytic H/D-exchange reactions were studied with [Ru(dtbpmp) (η2-H2)(H)2] (1) as catalyst. Under mild reaction conditions (25-75°C) a wide range of arenes and olefins undergo H/D exchange with [D6]benzene. A preference for protons at sp 2 carbons was observed with conversions up to >90% and significant regioselectivity in certain cases. For more reaction insights NMR-based kinetic studies were performed with naphthalene as substrate, revealing an activation energy of 15.8 kcal mol-1 for the H/D exchange at the β-position. Furthermore, the key steps of the reaction mechanism were investigated by means of DFT calculations for both model complexes (PMe 2 donor sites) and real catalysts (PtBu2 donor sites). The calculations resulted in Gibb's free activation energies in the range of 10-16 kcal mol-1, indicating H/D exchange at the β-position of naphthalene to be clearly favoured over the α-position, which is in full accordance with the experimental observations.

Original languageEnglish
Pages (from-to)3493-3500
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number22
DOIs
Publication statusPublished - Aug 2008

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Keywords

  • CH activation
  • Deuteration
  • DFT calculations
  • H/D exchange
  • Ruthenium dihydrogen complexes

ASJC Scopus subject areas

  • Inorganic Chemistry

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